全文获取类型
收费全文 | 928篇 |
免费 | 24篇 |
国内免费 | 3篇 |
专业分类
化学 | 724篇 |
晶体学 | 11篇 |
力学 | 16篇 |
数学 | 32篇 |
物理学 | 172篇 |
出版年
2023年 | 3篇 |
2022年 | 7篇 |
2021年 | 6篇 |
2020年 | 5篇 |
2019年 | 9篇 |
2018年 | 4篇 |
2017年 | 8篇 |
2016年 | 18篇 |
2015年 | 20篇 |
2014年 | 14篇 |
2013年 | 44篇 |
2012年 | 36篇 |
2011年 | 38篇 |
2010年 | 38篇 |
2009年 | 31篇 |
2008年 | 68篇 |
2007年 | 69篇 |
2006年 | 59篇 |
2005年 | 44篇 |
2004年 | 70篇 |
2003年 | 58篇 |
2002年 | 66篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 18篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 18篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 10篇 |
1973年 | 7篇 |
1969年 | 2篇 |
排序方式: 共有955条查询结果,搜索用时 15 毫秒
31.
The synthetic procedures for spilanthol and trail-following pheromone for a southern subterranean termite were described. The syntheses heavily depend on the new diene synthesis using titanium reagent. 相似文献
32.
Akiko Tsuhako Jing-Qian He Mariko Mihara Naoko Saino Sentaro Okamoto 《Tetrahedron letters》2007,48(52):9120-9123
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions. 相似文献
33.
The selective generation of three different silver-BINAP catalysts has been achieved via the proper combination of metal/ligand ratio and/or choice of silver salt. Indeed, the X-ray crystallographic study has been used to gain insight into the structure of the catalyst. After the evaluation of each species, 1:1 (AgX.(R)-BINAP) complex was found to be the real active species in the O-selective nitroso aldol reaction. On the other hand, a systematic survey of solvent has shown that the optimal 2:1 (AgX.(R)-BINAP) complex is the effective catalyst in the N-selective pathway. Thus, a new method of generation of the silver-BINAP catalyst and the synthetic transformations provide not only new insights into the developing area of catalytic enantioselective nitroso aldol synthesis but also clear guidance for the design of an effective catalyst. 相似文献
34.
New synthetic methods for the preparation of 1,3-dienes are described. 相似文献
35.
Toshio Morikawa Osama Bashir Abdel-Halim Hisashi Matsuda Osamu Muraoka Masayuki Yoshikawa 《Tetrahedron》2006,62(26):6435-6442
Three new pseudoguaiane-type sesquiterpenes, dichrocepholides A-C, and two new pseudoguaiane-type sesquiterpene dimers, dichrocepholides D and E, were isolated from the aerial part of Dichrocephala integrifolia. Their stereostructures were determined on the basis of chemical and physicochemical evidence. In addition, the extract and its principal sesquiterpene constituent, parthenin, showed an inhibitory activity on nitric oxide (NO) production and on induction of inducible NO synthase. 相似文献
36.
For 357 subshells of the 53 neutral atoms He through Xe in their ground states, the two-electron intracule (relative motion)
<u
k
>
nl
and extracule (center-of-mass motion) <R
k
>
nl
subshell moments in position space are examined as well as their counterparts <v
k
>
nl
and <P
k
>
nl
in momentum space, where n and l are the principal and azimuthal quantum numbers of the atomic subshell, respectively. It is clarified that between the intracule
and extracule moments the “2
k
-rule” is strictly valid, which means <u
k
>
nl
= 2
k
<R
k
>
nl
and <v
k
>
nl
= 2
k
<P
k
>
nl
for any nl subshell. Theoretical analysis also proves that for a particular case of k = +2, two relations <u
2>
nl
= (N
nl
−1)<r
2>
nl
and <v
2>
nl
= (N
nl
−1)<p
2>
nl
hold exactly, where N
nl
(≥2) is the number of electrons in the subshell nl, and <r
k
>
nl
and <p
k
>
nl
are the familiar one-electron subshell moments in position and momentum spaces, respectively. The latter equality establishes
a new and rigorous relation between the second electron-pair moments in momentum space and the total energy of an atom through
the virial theorem. For k=+1, −1, and −2, the numerical Hartree-Fock results for the 357 subshells show that there are approximate but accurate linear
relations between <u
k
>
nl
and <r
k
>
nl
and between <v
k
>
nl
and <p
k
>
nl
, in which the proportionality constant in each space depends on n,l, and k.
Received: 27 April 1998 / Accepted: 29 May 1998 / Published online: 28 August 1998 相似文献
37.
Morishita H Ohashi S Oku T Nakajima Y Kojima S Ryufuku M Nakamura H Ohmiya Y 《Photochemistry and photobiology》2002,75(3):311-315
Two marine dinoflagellates, Lingulodinium polyedrum and Pyrocystis lunula, emit light in a reaction involving the enzymatic oxidation of its tetrapyrrole luciferin by molecular oxygen. The characteristic properties of P. lunula luciferase have not been clarified, whereas L. polyedrum luciferase, which has three active domains, has been characterized. A cloned partial cDNA of the P. lunula luciferase encodes an active fragment corresponding to part of domain 2 and all of domain 3 of L. polyedrum luciferase. The homology of the amino acid sequence between the two luciferases in domain 3 is about 84.3%. A recombinant His-tagged luciferase fragment containing domain 3 (Mr = 46 kDa) catalyzed the light-emitting oxidation of luciferin (lambdamax = 474 nm). This protein was purified by a single affinity-chromatography procedure. The pH-activity profile and the bioluminescence spectrum of the recombinant enzyme having a third domain are almost identical to those of an extract from P. lunula cultured in vitro. The recombinant enzyme is active at pH 8.0, although the recombinant enzyme derived from the second domain of L. polyedrum luciferase is inactive at pH 8.0. Substitution of Glu-201 by histidine in the third domain of P. lunula luciferase showed a decrease of activity above pH 7.0, suggesting that histidine residues could be responsible for pH-sensitivity in dinoflagellate luciferase. 相似文献
38.
We report a simple preparation of Pd particles dispersed mesoporous carbons. The carbons were prepared by steam activation of carbonized vinylidene chloride/methyl acrylate copolymer (poly(VDC/MA)) containing yttrium acetylacetonate (Y(acac)(3)) and palladium acetylacetonate (Pd(acac)(2)). The resulting carbons consist of high contents of mesopore and uniformly dispersed fine Pd particles. We measured the catalytic activities of the carbons obtained for hydrogenation of methyl linoleate. The Pd particles dispersed in mesoporous activated carbons obtained from poly(VDC/MA) containing both Y(acac)(3) and Pd(acac)(2) showed high catalytic activities, compared with the microporous activated carbon obtained from poly(VDC/MA) containing only Pd(acac)(2). Especially Pd particles dispersed in mesoporous carbons exhibited excellent selectivity for hydrogenation of diene (methyl linoleate) to monoene (methyl oleate). 相似文献
39.
The infrared spectra of the water-nitrogen complexes trapped in argon matrices have been studied with Fourier transform infrared absorption spectroscopy. The absorption lines of the H20-N2 1:1, 1:2, 1:n, and 2:1 complexes have been confirmed on the basis of the concentration effects. In addition, we have observed a few lines and propose the assignments for the 2:2, 2:3, and 2:4 complexes in the nu1 symmetric stretching and nu2 bending regions of the proton-acceptor molecule, and in the bonded OH stretching region of the proton-donor molecule. The redshifts in the bonded OH stretching mode and blueshifts in the OH bending mode suggest that the hydrogen bonds in the (H2O)2-(N2)n complexes with n = 1-4 are strengthened by the cooperative effects compared to the pure H2O dimer. Two absorption bands due to the 3:n complexes are also observed near the bonded OH stretching region of the H2O trimer. 相似文献
40.
Fukuji Higashi Yuko Mihara Ikuo Takahashi Wen-Hsin Chen Tech-Chou Chang 《Journal of polymer science. Part A, Polymer chemistry》1985,23(11):2851-2856
The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols. 相似文献